US2023090892A1PendingUtilityA1

Solid electrolyte, method of preparing the same, and lithium battery including the solid electrolyte

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Assignee: SAMSUNG ELECTRONICS CO LTDPriority: Aug 4, 2017Filed: Nov 11, 2022Published: Mar 23, 2023
Est. expiryAug 4, 2037(~11 yrs left)· nominal 20-yr term from priority
Inventors:Jusik KimMichael Edward BaddingHyunseok KimZhen SongTaehwan Yu
H01M 10/052H01M 4/405Y02P70/50H01M 10/058H01M 50/403H01M 4/382H01M 50/431H01M 2004/027H01M 10/0564H01M 2300/0068H01M 2300/0071Y02E60/10H01M 10/0562H01M 2300/0094H01M 10/0525H01B 1/06H01M 2300/0077
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Claims

Abstract

A solid electrolyte including: a lithium ion inorganic conductive layer; and an amorphous phase on a surface of the lithium ion inorganic conductive layer, wherein the amorphous phase is an irradiation product of the lithium ion inorganic conductive layer. Also, the method of preparing the same, and a lithium battery including the solid electrolyte.

Claims

exact text as granted — not AI-modified
What is claimed is: 
     
         1 . A solid electrolyte, comprising:
 a lithium ion inorganic conductive layer; and   an amorphous phase on a surface of the lithium ion inorganic conductive layer,   wherein the amorphous phase is in a form of an amorphous film,   wherein the amorphous film has a surface area of about 35 cm 2 /cm 3  to about 1×10 6  cm 2 /cm 3 , and   wherein a thickness ratio of the lithium ion inorganic conductive layer to the amorphous film is from 1:0.001 to 1:0.2.   
     
     
         2 . The solid electrolyte of  claim 1 , wherein the amorphous phase is in a form of an amorphous film having a thickness of about 5 nanometers to about 5 micrometers. 
     
     
         3 . The solid electrolyte of  claim 2 , further comprising a semi-crystalline film comprising a semi-crystalline phase, wherein the semi-crystalline film is situated between the lithium ion inorganic conductive layer and the amorphous film, and wherein the semi-crystalline film has a thickness less than a thickness of the amorphous film. 
     
     
         4 . The solid electrolyte of  claim 3 , further comprising a crystalline phase situated between the semi-crystalline film and the amorphous film. 
     
     
         5 . The solid electrolyte of  claim 1 , wherein the amorphous film is in a form of a patterned amorphous film. 
     
     
         6 . The solid electrolyte of  claim 1 , wherein and the patterned amorphous film has a surface area of about 200 percent to about 500 percent greater than a surface area of a same solid electrolyte in which the amorphous phase is not present. 
     
     
         7 . The solid electrolyte of  claim 5 , wherein the patterned amorphous film has a shape comprising at least one of a plurality of perpendicular lines and a plurality of parallel lines, and wherein the perpendicular or parallel lines comprise lines having a line width of from about 10 micrometers to about 30 micrometers 
     
     
         8 . The solid electrolyte of  claim 1 , wherein the lithium ion inorganic conductive layer comprises at least one of a garnet compound, an argyrodite compound, a lithium super ionic conductor, a sodium super ionic conductor, lithium nitride, lithium hydride, a compound having a perovskite structure, and a lithium halide. 
     
     
         9 . The solid electrolyte of  claim 8 , wherein the lithium ion inorganic conductive layer comprises at least one of:
 a garnet ceramic of the formula Li 3+x La 3 M 2 O 12  wherein 0≤x≤5, and M is tellurium, niobium, or zirconium,   Li 1+x+y Al x Ti 2−x Si y P 3−y O 12  wherein 0<x<2 and 0≤y<3,   BaTiO 3 ,   Pb(Zr 1−x Ti x )O 3  wherein 0<x<1,   Pb 1−x La x Zr 1−y Ti y O 3  wherein 0≤x<1 and 0≤y<1,   Pb(Mg 1/3 Nb 2/3 )O 3 —PbTiO 3 ,   Li 3 PO 4 ,   Li x Ti y (PO 4 ) 3  wherein 0<x<2 and 0<y<3,   Li x Al y Ti z (PO4) 3  wherein 0<x<2, 0<y<1, and 0<z<3,   Li 1+x+y (Al a Ga 1−a ) x (Ti b Ge 1−b ) 2−x Si y P 3−y O 12  wherein 0≤x≤1, 0≤y≤1, 0≤a≤1, and 0≤b≤1,   Li x La y TiO 3  wherein 0<x<2 and 0<y<3,   Li x Ge y P z S w  wherein 0<x<4, 0<y<1, 0<z<1, and 0<w<5,   Li x N y  wherein 0<x<4 and 0<y<2,   a glass of the formula Li x Si y S z  glass wherein 0≤x<3, 0<y<2, and 0<z<4,   a glass of the formula Li x P y S z  glass wherein 0≤x<3, 0<y<3, and 0<z<7,   Li 3x La 2/3-x TiO 3  wherein 0≤x≤1/6,   Li 1+y Al y Ti 2−y (PO 4 ) 3  wherein 0≤y≤1,   Li 1+z Al z Ge 2−z (PO 4 ) 3  wherein 0≤z≤1,   Li 2 O, LiF, LiOH, Li 2 CO 3 , LiAlO 2 , a (Li 2 O) a —(Al 2 O 3 ) b —(SiO 2 ) c —(P 2 O 5 ) d —(TiO 2 ) e —(GeO 2 ) f  ceramic wherein 0≤a≤1, 0b≤1, 0≤c≤1, 0≤d≤1, 0≤e≤1, and 0≤f≤1, Li 7 La 3 Zr 2 O 12 , Li 10 GeP 2 S 12 , Li 3.25 Ge 0.25 P 0.75 S 4 , Li 3 PS 4 , Li 6 PS 5 Br, Li 6 PS 5 Cl, Li 7 PS 5 , Li 6 PS 5 I, Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , LiTi 2 (PO 4 ) 3 , LiGe 2 (PO 4 ) 3 , LiHf 2 (PO 4 ) 3 , LiZr 2 (PO 4 ) 3 , Li 2 NH 2 , Li 3 (NH 2 ) 2 I, LiBH 4 , LiAlH 4 , LiNH 2 , Li 0.34 La 0.51 TiO 2.94 , LiSr 2 Ti 2 NbO 9 , Li 0.06 La 0.66 Ti 0.93 Al 0.03 O 3 , Li 0.34 Nd 0.55 TiO 3 , Li 2 CdCl 4 , Li 2 MgCl 4 , Li 2 ZnI 4 , and Li 2 CdI 4 .   
     
     
         10 . The solid electrolyte of  claim 8 , wherein the lithium ion inorganic conductive layer comprises at least one compound selected from a compound of Formula 1 and a compound of Formula 1 a:
   Li 7−x M 1   x La 3−a M 2   a Zr 2−b M 3   b O 12    Formula 1
     Li 7−x La 3−a M 2   a Zr 2−b M 3   b O 12    Formula 1a
   wherein, in Formula 1, M 1  comprises at least one of gallium and aluminum,   in Formulas 1 and 1a, M 2  comprises at least one calcium, strontium, cesium, and barium,   M 3  comprises at least one of aluminum, tungsten, niobium, and tantalum, and   0≤x<3, 0≤a≤3, and 0≤b<2.   
     
     
         11 . The solid electrolyte of  claim 10 , wherein a dopant is the M 1 , M 2 , and M 3  of Formulas 1 and 1a, and
 wherein a total content of the dopant in the amorphous phase is equal to or less than 1 mole percent, based on 100 mole percent of the amorphous phase.   
     
     
         12 . The solid electrolyte of  claim 10 , wherein the compound of Formula 1 is at least one of Li 4.9 La 2.5 Ca 0.5 Zr 1.7 Nb 0.3 O 12 , Li 4.9 Ga 0.5+δ La 3 Zr 1.7 W 0.3 O 12  wherein 0≤δ≤1.6, Li 6.4 La 3 Zr 1.7 W 0.3 O 12 , Li 7 La 3 Zr 1.5 W 0.5 O 12 , Li 7 La 2.75 Ca 0.25 Zr 1.75 Nb 0.25 O 12 , Li 7 La 3 Zr 1.5 Nb 0.5 O 12 , Li 7 La 3 Zr 1.5 Ta 0.5 O 12 , Li 6.272 La 3 Zr 1.7 W 0.3 O 12 , and Li 5.39 Ga 0.5+δ La 3 Zr 1.7 W 0.3 O 12  wherein 0≤δ≤1.1. 
     
     
         13 . The solid electrolyte of  claim 1 , wherein the solid electrolyte is a liquid-impermeable layer having a porosity of 30% or less. 
     
     
         14 . The solid electrolyte of  claim 1 , wherein a thickness of the solid electrolyte is about 1 micrometer to about 300 micrometers. 
     
     
         15 . A lithium battery comprising:
 a negative electrode;   a positive electrode; and   the solid electrolyte of  claim 1  between the negative electrode and the positive electrode.   
     
     
         16 . The lithium battery of  claim 15 , wherein the amorphous phase of the solid electrolyte is adjacent to the negative electrode,
 the amorphous phase of the solid electrolyte is adjacent to the negative electrode, or   the amorphous phase of the solid electrolyte is adjacent to the negative electrode and the positive electrode.   
     
     
         17 . The lithium battery of  claim 15 , wherein the negative electrode is a lithium metal negative electrode comprising lithium metal or a lithium metal alloy. 
     
     
         18 . The lithium battery of  claim 15 , wherein an interfacial resistance between the lithium metal negative electrode and the solid electrolyte is about 10 ohm cm 2  to about 500 ohm cm 2 . 
     
     
         19 . A method of preparing a solid electrolyte, the method comprising:
 providing a lithium ion inorganic conductive layer; and   irradiating the lithium ion inorganic conductive layer with a laser beam to form an amorphous phase on a surface of the lithium ion inorganic conductive layer to prepare the solid electrolyte of  claim 1 ,   wherein the irradiating comprises directing the laser beam to form a pattern on the lithium ion inorganic conductive layer, wherein a surface area of the amorphous phase is about 200% to about 500% of a surface area of the lithium ion inorganic conductive layer prior to irradiation.   
     
     
         20 . A solid electrolyte, comprising:
 a lithium ion conductive layer comprising a lithium ion conductive garnet; and   an amorphous lithium-lanthanum-zirconium oxide on a surface of the lithium ion conductive layer,   wherein the amorphous lithium-lanthanum-zirconium oxide is in a form of an amorphous film,   wherein the amorphous film has a surface area of about 35 cm 2 /cm 3  to about 1×10 6  cm 2 /cm 3 , and   wherein a thickness ratio of the lithium ion inorganic conductive layer to the a morphous film is from 1:0.001 to 1:0.2.

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